Transition‐Metal‐Doped NIR‐Emitting Silicon Nanocrystals

Impurity-doping in nanocrystals significantly affects their electronic properties and diversifies their applications. Herein, we report the synthesis of transition metal (Mn, Ni, Co, Cu)-doped oleophilic silicon nanocrystals (SiNCs) through hydrolysis/polymerization of triethoxysilane with acidic aqueous metal salt solutions, followed by thermal disproportionation of the resulting gel into a doped-Si/SiO2 composite that, upon HF etching and hydrosilylation with 1-n-octadecene, produces free-standing octadecyl-capped doped SiNCs (diameter≈3 to 8 nm; dopant <0.2 atom %). Metal-doping triggers a red-shift of the SiNC photoluminescence (PL) of up to 270 nm, while maintaining high PL quantum yield (26 % for Co doping).